PEO-b-P4VP摻混P4VP混合物之低臨界有序化現象研究

簡易檢索 / 詳目顯示

回結果列表

研究生：	許長正 Shiu, Chang-Cheng
論文名稱：	PEO-b-P4VP摻混P4VP混合物之低臨界有序化現象研究 Self-assembly of PEO-b-P4VP and Its Blends with P4VP Homopolymer Displaying LCOT Behavior
指導教授：	陳信龍 Chen, Hsin-Lung
口試委員:	曹正熙孫亞賢
學位類別：	碩士 Master
系所名稱：	工學院 - 化學工程學系 Department of Chemical Engineering
論文出版年：	2014
畢業學年度：	102
語文別：	英文
論文頁數：	48
中文關鍵詞：	低臨界有序-無序相轉化、雙嵌段高分子摻混單嵌段高分子混合物、乾-濕型溶解、平均場理論
外文關鍵詞：	LCOT, Mixtures of block polymer with homopolymer, wet-dry brush, mean-field theory
相關次數：	點閱：2 下載：0
分享至:	分享至facebook 分享至twitter

查詢本校圖書館目錄查詢臺灣博碩士論文知識加值系統勘誤回報

利用變溫小角度X光散射，我們發現與探討了對稱的雙嵌段高分子聚氧乙烯-聚四乙烯吡啶(poly(ethylene oxide)-block-poly (4-vinylpyridine), PEO-b-P4VP)呈現有序-無序的相轉化(order-disorder transition, ODT)是低臨界有序化(Lower critical ordering transition, LCOT)的相行為，以及其與單嵌段高分子聚氧乙烯-聚四乙烯吡啶(Homopoly4VP, H4VP)所形成的混合物中，H4VP溶解進P4VP的行為。PEO-b-P4VP的ODT發生於降溫過程，當溫度接近相轉化溫度(TODT)時，大範圍有序的結構仍保持良好，這代表著傳統高臨界有序化(upper critical ordering transition, UCOT)相行為在ODT時所產生嚴重的熱擾動，於PEO-b-P4VP的LCOT中不再具有影響力，而此種LCOT是比較接近平均場理論的有序-無序相轉化行為。當H4VP與摻混進PEO-b-P4VP，PEO-b-P4VP仍呈現LCOT的相行為，且在微相分離的高溫下H4VP會溶解進入P4VP的微相中，在不同分子量的H4VP情況，形成濕型或乾型的溶解方式(wet-dry brush)，進而影響到其層狀的厚度，相較於典型的聚苯乙烯-聚異戊二烯(polystyrene-b-polyisoprene, PS-b-PI)，區分wet-dry brush的參數r (MH4VP/MB4VP)遠小於傳統上PS-b-PI所定義的1，這是由於在高溫的情況下，表面能和亂度同時扮演主導結構的角色，因此阻礙了H4VP均勻分散的企圖，為求不讓表面能過大，儘管摻混大量的H4VP使其4VP體積分率達到0.7，PEO-b-P4VP仍保持著層狀的結構。

We have investigated the order-disorder transition (ODT) of a lamellae-forming PEO-b-P4VP exhibiting LCOT behavior and examined the solubilization behavior of P4VP homopolymer in its blends with the PEO-b-P4VP. PEO-b-P4VP exhibited ODT upon cooling. The temperature-dependent SAXS measurement revealed that as the TODT was approached on cooling, the long-range order of the lamellar structure was still well preserved, indicating that the thermal noise effect, which is prevalent in the conventional UCOT system, did not play a major role, such that the phase transition process may approach the mean-field behavior. When its blends with H4VP, which can be solubilized into the P4VP microdomains, also displayed LCOT behavior, where they showed a order-to-disorder transition (ODT) upon cooling. In the microphase-separated state, the interdomain distance D of the lamellae structure was found to increase with increasing molecular weight of H4VP (MH4VP) and the H4VP formed wet or dry brush solubilization. In contrast to the classical system of PS-b-PI / homopolymer blends, the critical value of r (MH4VP/MB4VP) below which the system shows completely wet brush behavior was found to lie significantly lower than 1.0. This phenomenon was attributed to the enhanced roles of both repulsive interaction energy and conformational entropy at high temperature, so as to hinder the uniform solubilization of H4VP. Even when the H4VP was uniformly solubilized in the P4VP microdomain, the lamellae morphology remained stable even when the overall P4VP composition was highly unsymmetric.

致謝    I
Abstract    II
摘要    III
Table of Contents    IV
List of Tables    V
List of Figures    VI
Chapter 1 Introduction    1
1.1 Phase Behavior of Block Copolymer    1
1.2 Melt Phase Behavior of Block Copolymer Binary Blend    5
1.3 Lower Critical Ordering Transition of Block Copolymer    9
1.4 Motivation and Objectives of the Study    12
Chapter 2 Experimental Section    13
2.1 Materials    13
2.2 Preparation of blends    15
2.3 Characterization    17
2.3-1 Small and Wide Angle X-ray Scattering (SWAXS) Measurements.    17
2.3-2 Transmission Electron Microscopy (TEM) Measurements.    17
Chapter 3 Results and Discussion    18
3.1 Thermally-induced Lower Critical Ordering Transition (LCOT) Behavior of PEO-b-P4VP    18
3.2 Phase Behavior of PEO-b-P4VP/H4VP Blends    34
3.3 Effect of H4VP molecular weight on the phase behavior of PEO-b-P4VP/H4VP    37
Chapter 4 Conclusions    45
Chapter 5 References    47

                                

1. Hamley, I. W., The Physics of Block Copolymers. Oxford University Press, Incorporated: 1998.
2. Hamley, I. W., Developments in block copolymer science and technology. J. Wiley: Chichester, West Sussex; Hoboken, NJ, 2004.
3. Bates, F. S.; Fredrickson, G. H. Physics Today 1999, 52, (2), 32-38.
4. Anne-Valérie, R.; Ludwik, L. Nature Materials 2005, 4, (1), 19-31.
5. Meier, D. J. Journal of Polymer Science Part C: Polymer Symposia 1969, 26, (1), 81-98.
6. Leary, D. F.; Williams, M. C. Journal of Polymer Science Part B: Polymer Letters 1970, 8, (5), 335-340.
7. Leary, D. F.; Williams, M. C. Journal of Polymer Science: Polymer Physics Edition 1973, 11, (2), 345-358.
8. Leary, D. F.; Williams, M. C. Journal of Polymer Science: Polymer Physics Edition 1974, 12, (2), 265-287.
9. Helfand, E. Macromolecules 1975, 8, (4), 552-556.
10. Matsen, M. W.; Bates, F. S. Journal of Polymer Science Part B: Polymer Physics 1997, 35, (6), 945-952.
11. Leibler, L. Macromolecules 1980, 13, (6), 1602-1617.
12. Matsen, M. W.; Bates, F. S. Macromolecules 1996, 29, (4), 1091-1098.
13. Tanaka, H.; Hasegawa, H.; Hashimoto, T. Macromolecules 1991, 24, (1), 240-251.
14. Koizumi, S.; Hasegawa, H.; Hashimoto, T. Makromol Chem-M Symp 1992, 62, 75-91.
15. Hashimoto, T.; Tanaka, H.; Hasegawa, H. Macromolecules 1990, 23, (20), 4378-4386.
16. Hsu, J.-Y.; Nandan, B.; Chen, M.-C.; Chiu, F.-C.; Chen, H.-L. Polymer 2005, 46, (25), 11837-11843.
17. Ruzette, A. V. G.; Mayes, A. M. Macromolecules 2001, 34, (6), 1894-1907.
18. Ruzette, A.-V.; Banerjee, P.; Mayes, A.; Russell, T. The Journal of Chemical Physics 2001, 114, 8205.
19. Cowie, J. M. K. G.; Arrighi, V., Polymers: chemistry and physics of modern materials. CRC Press: 2008.
20. Pollard, M.; Russell, T. P.; Ruzette, A. V.; Mayes, A. M.; Gallot, Y. Macromolecules 1998, 31, (19), 6493-6498.
21. Yeung, C.; Desai, R. C.; Shi, A.-C.; Noolandi, J. Physical review letters 1994, 72, 1834-1834.
22. Russell, T.; Karis, T.; Gallot, Y.; Mayes, A. 1994.
23. Du Yeol Ryu, U. J.; Kim, J. K.; Russell, T. P. Nature materials 2002, 1, (2), 114-117.
24. Ryu, D. Y.; Park, M. S.; Chae, S. H.; Jang, J.; Kim, J. K.; Russell, T. P. Macromolecules 2002, 35, (23), 8676-8680.
25. Ryu, D. Y.; Jeong, U.; Lee, D. H.; Kim, J.; Youn, H. S.; Kim, J. K. Macromolecules 2003, 36, (8), 2894-2902.
26. Yeh, C.-L.; Hou, T.; Chen, H.-L.; Yeh, L.-Y.; Chiu, F.-C.; Müller, A. J.; Hadjichristidis, N. Macromolecules 2011, 44, (3), 440-443.
27. Lee, R.-T. 2013.
28. Hashimoto, T.; Tsukahara, Y.; Kawai, H. Macromolecules 1981, 14, (3), 708-715.
29. Hashimoto, T.; Kowsaka, K.; Shibayama, M.; Kawai, H. Macromolecules 1986, 19, (3), 754-762.

全文公開日期本全文未授權公開 (校內網路)
全文公開日期本全文未授權公開 (校外網路)

簡易檢索 / 詳目顯示

相關論文